Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Isolation and Versatile Derivatization of an Unsaturated Anionic Silicon Cluster (Siliconoid).

ABSTRACT: The characteristic features of bulk silicon surfaces are echoed in the related partially substituted-and thus unsaturated-neutral silicon clusters (siliconoids). The incorporation of siliconoids into more-extended frameworks is promising owing to their unique electronic features, but further developments in this regard are limited by the notable absence of functionalized siliconoid derivatives until now. Herein we report the isolation and full characterization of the lithium salt of an anionic R5 Si6 -siliconoid, thus providing the missing link between silicon-based Zintl anions and siliconoid clusters. Proof-of-principle for the high potential of this species for the efficient transfer of the intact unsaturated R5 Si6 moiety is demonstrated by clean reactions with representative electrophiles of Groups?13, 14, and 15.

SUBMITTER: Willmes P

PROVIDER: S-EPMC4770444 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Isolation and Versatile Derivatization of an Unsaturated Anionic Silicon Cluster (Siliconoid).

Willmes Philipp P Leszczyńska Kinga K Heider Yannic Y Abersfelder Kai K Zimmer Michael M Huch Volker V Scheschkewitz David D

Angewandte Chemie (International ed. in English) 20160122 8

The characteristic features of bulk silicon surfaces are echoed in the related partially substituted-and thus unsaturated-neutral silicon clusters (siliconoids). The incorporation of siliconoids into more-extended frameworks is promising owing to their unique electronic features, but further developments in this regard are limited by the notable absence of functionalized siliconoid derivatives until now. Herein we report the isolation and full characterization of the lithium salt of an anionic R ...[more]

PMID: 26800440

Similar Datasets

A highly unsaturated six-vertex amido-substituted silicon cluster.

Project description:Thermal treatment of the bicyclo[1.1.0]tetrasilatetraamide [Si4{N(SiMe3)Dipp}4] 1 resulted in the formation of a highly unsaturated six-vertex silicon cluster [Si6{N(SiMe3)Dipp}4] 2 with only four amine-substituents and two ligand-free silicon atoms. In solution, a major and a minor conformer of this cluster are in equilibrium according to multinuclear NMR spectroscopy, lineshape analysis, DFT calculations and molecular dynamics simulations. The bonding situation in the highly unsaturated cluster features lone pair type character at the ligand-free silicon atoms and partial single and double bond character in the upper butterfly-shaped ring of 2. This allows to consider 2 as the silicon analogue of a butalene isomer.

| S-EPMC7448375 | biostudies-literature

Atomically Precise Expansion of Unsaturated Silicon Clusters.

Project description:Small- to medium-sized clusters occur in various areas of chemistry, for example, as active species of heterogeneous catalysis or as transient intermediates during chemical vapor deposition. The manipulation of stable representatives is mostly limited to the stabilizing ligand periphery, virtually excluding the systematic variation of the property-determining cluster scaffold. We now report the deliberate expansion of a stable unsaturated silicon cluster from six to seven and finally eight vertices. The consecutive application of lithium/naphthalene as the reducing agent and decamethylsilicocene as the electrophilic source of silicon results in the expansion of the core by precisely one atom with the potential of infinite repetition.

| S-EPMC6563707 | biostudies-literature

Online photochemical derivatization enables comprehensive mass spectrometric analysis of unsaturated phospholipid isomers.

Project description:Mass spectrometry-based lipidomics is the primary tool for the structural analysis of lipids but the effective localization of carbon-carbon double bonds (C=C) in unsaturated lipids to distinguish C=C location isomers remains challenging. Here, we develop a large-scale lipid analysis platform by coupling online C=C derivatization through the Paternò-Büchi reaction with liquid chromatography-tandem mass spectrometry. This provides rich information on lipid C=C location isomers, revealing C=C locations for more than 200 unsaturated glycerophospholipids in bovine liver among which we identify 55 groups of C=C location isomers. By analyzing tissue samples of patients with breast cancer and type 2 diabetes plasma samples, we find that the ratios of C=C isomers are much less affected by interpersonal variations than their individual abundances, suggesting that isomer ratios may be used for the discovery of lipid biomarkers.

| S-EPMC6325166 | biostudies-literature

Versatile ultrathin nanoporous silicon nitride membranes.

Project description:Single- and multiple-nanopore membranes are both highly interesting for biosensing and separation processes, as well as their ability to mimic biological membranes. The density of pores, their shape, and their surface chemistry are the key factors that determine membrane transport and separation capabilities. Here, we report silicon nitride (SiN) membranes with fully controlled porosity, pore geometry, and pore surface chemistry. An ultrathin freestanding SiN platform is described with conical or double-conical nanopores of diameters as small as several nanometers, prepared by the track-etching technique. This technique allows the membrane porosity to be tuned from one to billions of pores per square centimeter. We demonstrate the separation capabilities of these membranes by discrimination of dye and protein molecules based on their charge and size. This separation process is based on an electrostatic mechanism and operates in physiological electrolyte conditions. As we have also shown, the separation capabilities can be tuned by chemically modifying the pore walls. Compared with typical membranes with cylindrical pores, the conical and double-conical pores reported here allow for higher fluxes, a critical advantage in separation applications. In addition, the conical pore shape results in a shorter effective length, which gives advantages for single biomolecule detection applications such as nanopore-based DNA analysis.

| S-EPMC2795523 | biostudies-literature

Chalcogen-Expanded Unsaturated Silicon Clusters: Thia-, Selena-, and Tellurasiliconoids.

Project description:Reactions of silylenes with heavier chalcogens (E) typically result in Si=E double bonds or their π-addition products. In contrast, the oxidation of a silylene-functionalized unsaturated silicon cluster (siliconoid) with Group 16 elements selectively yields cluster expanded siliconoids Si7 E (E=S, Se, Te) fully preserving the unsaturated nature of the cluster scaffold as evident from the NMR signatures of the products. Mechanistic considerations by DFT calculations suggest the intermediacy of a Si6 siliconoid with exohedral Si=E functionality. The reaction thus may serve as model system for the oxidation of surface-bonded silylenes at Si(100) by chalcogens and their diffusion into the silicon bulk.

| S-EPMC7756652 | biostudies-literature

Imaging and Analysis of Isomeric Unsaturated Lipids through Online Photochemical Derivatization of Carbon-Carbon Double Bonds*.

Project description:Unraveling the complexity of the lipidome requires the development of novel approaches for the structural characterization of lipid species with isomer-level discrimination. Herein, we introduce an online photochemical approach for lipid isomer identification through selective derivatization of double bonds by reaction with singlet oxygen. Lipid hydroperoxide products are generated promptly after laser irradiation. Fragmentation of these species in a mass spectrometer produces diagnostic fragments revealing the C=C locations in the unreacted lipids. This approach uses an inexpensive light source and photosensitizer making it easy to incorporate into any lipidomics workflow. We demonstrate the utility of this approach for the shotgun profiling of C=C locations in different lipid classes present in tissue extracts using electrospray ionization (ESI) and ambient imaging of lipid species differing only by the location of C=C bonds using nanospray desorption electrospray ionization (nano-DESI).

| S-EPMC8815435 | biostudies-literature

Isolation of an Anionic Dicarbene Embedded Sn2 P2 Cluster and Reversible CO2 Uptake.

Project description:Decarbonylation of a cyclic bis-phosphaethynolatostannylene [(ADC)Sn(PCO)]2 based on an anionic dicarbene framework (ADC = PhC{N(Dipp)C}2 ; Dipp = 2,6-iPr2 C6 H3 ) under UV light results in the formation of a Sn2 P2 cluster compound [(ADC)SnP]2 as a green crystalline solid. The electronic structure of [(ADC)SnP]2 is analyzed by quantum-chemical calculations. At room temperature, [(ADC)SnP]2 reversibly binds with CO2 and forms [(ADC)2 {SnOC(O)P}SnP]. [(ADC)SnP]2 enables catalytic hydroboration of CO2 and reacts with elemental selenium and Fe2 (CO)9 to afford [(ADC)2 {Sn(Se)P2 }SnSe] and [(ADC)Sn{Fe(CO)4 }P]2 , respectively. All compounds are characterized by multinuclear NMR spectroscopy and their solid-state molecular structures are determined by single-crystal X-ray diffraction.

| S-EPMC10837339 | biostudies-literature

Intramolecular oxamidation of unsaturated O-alkyl hydroxamates: a remarkably versatile entry to hydroxy lactams.

Project description:The development of a versatile method for the preparation of five- to eight-membered hydroxy lactams that involves the iodine(III)-mediated oxamidation of unsaturated O-alkyl hydroxamates is described. This transformation, which is believed to proceed through the intermediacy of singlet nitrenium and bicyclic N-acyl-N-alkoxyaziridinium ions, is both stereospecific and highly regioselective in most of the 22 cases examined.

| S-EPMC2812663 | biostudies-literature

Versatile Approach of Silicon Nanofabrication without Resists: Helium Ion-Bombardment Enhanced Etching.

Project description:Herein, we report a helium ion-bombardment enhanced etching method for silicon nanofabrication without the use of resists; furthermore, we demonstrate its unique advantages for straightforward fabrication on irregular surfaces and prototyping nano-electro-mechanical system devices, such as self-enclosed Si nanofluidic channels and mechanical nano-resonators. This method employs focused helium ions to selectively irradiate single-crystal Si to disrupt the crystal lattice and transform it into an amorphous phase that can be etched at a rate 200 times higher than that of the non-irradiated Si. Due to the unique raindrop shape of the interaction volumes between helium ions and Si, buried Si nanofluidic channels can be constructed using only one dosing step, followed by one step of conventional chemical etching. Moreover, suspended Si nanobeams can be fabricated without an additional undercut step for release owing to the unique raindrop shape. In addition, we demonstrate nanofabrication directly on 3D micro/nano surfaces, such as an atomic force microscopic probe, which is challenging for conventional nanofabrication due to the requirement of photoresist spin coating. Finally, this approach can also be extended to assist in the etching of other materials that are difficult to etch, such as silicon carbide (SiC).

| S-EPMC9565762 | biostudies-literature

Halogenation of carbyne complexes: isolation of unsaturated metallaiodirenium ion and metallabromirenium ion.

Project description:The halogenation of metallapentalyne led to the formation of metallapentalenes, which were fully characterized and studied by DFT calculations. The experimental and computational studies indicate that four resonance forms contribute to the overall structure of the metallapentalenes, and one resonance form could be viewed as the first examples of metallaiodirenium and metallabromirenium ions.

| S-EPMC5604402 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data